NZ200137A

NZ200137A - Elastomer-containing,initially erasable ballpoint pen ink

Info

Publication number: NZ200137A
Application number: NZ200137A
Authority: NZ
Inventors: F A Muller
Original assignee: Scripto Inc
Priority date: 1981-03-26
Filing date: 1982-03-25
Publication date: 1985-11-08
Also published as: KR830009178A; ES510746A0; IN158097B; GB2095692A; ES8307276A1; JPS57170968A; MX160265A; PH17397A; EP0061886A1; KR900000298B1; GB2095692B; AU8180482A; CA1211579A; US4349639A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £00137 I 2 00137 Priority Oats(s): Complete Specification Filed: Class: . '! j £2 { Publication Date: I jfe" NOV 19951 P.O. Journal, No: 77., Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "METHOD OF MAKING AND THE COMPOSITION FORAN INITIALLY ERASABLE INK FOR A BALL POINT WRITING INSTRUMENT" "I~/WE SCRIPTO, INC. a Georgia corporation, of 7012 Bestfriend Road, Doraville, Georgia 30340, U.S.A. hereby declare the invention, for which I/we pray that a patent may be granted to me/us, and the method by which it is to be performed, to be particularly described in and by the following statement:— 200137 BACKGROUND OF THE INVENTION 1. Field of the Invention. The present invention pertains to a rr.ethod of making an the composition for an initially erasable ink for a ball point writinq instrument which ink is characterized by its initial prasability by ordinary pencil erasers when applied by a ball point writing instrument to an absorbent paper or paperlike „wr.iting surface and which thereafter develops permanence. 2. .Description of the Prior Art. Many freouently interrelated factors must be taken into account in the formulation of a writing medium. These factors fall into two categories, namely, those which stem from the type writinq instruments to be used in dispensing the writing medium onto the writinq surface, and those which are concerned with the desired characteristics that the writing medium possesses after being dispensed. 2 2001 3 The principal type of writing instrument that is to be used with the ink composition of the present invention is a ball point writinq instrument. I i i Insofar as the characteristics of the writinq medium in j i I the "after dispensed" state are concerned, appearance and relative; indelibility are the most important. In most cases, the appearance of the writing medium means little more than the color j of the written line. Indelibility is related to the ease of j removal of the written line. Thus, an indelible writing medium is one which is resistant to removal from the writing surface. Obtainment of a high deqree of indelibility is not always necessarily desirable. In some instances one may want a i writing medium which immediately is not easily removable by mechanical means from the writinq surface, while in other instances one may want a writing medium which at least initially is easily removable but which may attain permanence or indelibility over an extended period of time, as for example, over! i a period of hours. If such a medium is to be considered as being truly erasable, it must be readily removable at least during an initial period of time from the substratum to which it has been applied without any damage of any significant degree to the area of the substratum involved. In order to understand the nature of this invention, consideration must first be given to the conditions which the formulator of an erasable writing medium must avoid. This in turn requires at least an elementary knowledge of the structure of paper, since paper is the substratum most commonly employed as a writinq surface. 3 -A<- 2001Zf Paper is essentially a mat of randomly oriented cellulose fibers. Thus, paper consists of solid structural | members, namely the cellulose fibers, having numerous minute voids! I therebetween. From the description, it may readily be seen that j I the formulator or designer of an erasable writing medium must ; prevent the colorant portion of the medium from penetrating to anv| substantial degree into the voids in the surface being written ! upon because if there is substantial penetration into the voids the suhseauent removal of the colorant by mechanical means cannot be accomplished without damage to the writing surface. Likewise, : i it may readily be seen that for a writing medium to be erasable, I i the colorant particles must be prevented from affixing themselves ; with any substantial degree of permanence, either by chemical i reaction or as a result of mere physical attraction, to the solid I members of the paper substratum. j I In the nast, attempts to achieve an erasable writing j medium for a ball point pen usually have been unsuccessful. j Of course, one may use a superabrasive eraser to remove ordinary i ball pen inks from the paper substratum normally used for writing I I ! purposes. As discussed above, such substratum is porous to some { degree and the ball pen inks in ordinary usage tend to penetrate j those pores. In addition, the colorants in such inks tend to \ affix themselves to the fibers which constitute the solid portion ! i I of the substratum. Therefore, the only way to erase markings madej with ordinary ball pen inks is to physically remove a substantial \ number of the fibers in the vicinity of the markings. As a | result, the paper substratum is generally so damaged during the j erasure process that it is rendered unsuitable for any further use! as a writing surface. i | j f I -£T- \ 2 0 013 7 i Attempts have been made to modify ordinary ball pen ink so as to prevent the colorant portion thereof from penetrating thej pores of the paper substratum. These attempts consisted of j substituting pigment-type colorants for the dye-type colorants \ normally used in ball pen inks. The reasoning behind this i approach was that since pigment-type colorants normally have a greater particle size than dye-type colorants, the pigment-type I colorants would become substantially immobile on deposition upon j the surface of the paper substratum and, therefore would not tend | to penetrate into the pores of the paper. However, this line of j reasoning overlooked the fact that in a ball point writing I instrument, the ink is dispensed through a very minute clearance between the ball and socket and that any pigment-type particle which is small enough to be so dispensed will tend to behave as if it were a dye-type particle. Therefore, the colorant portion of such inks was not immobilized to any significant degree and as a j i consequence, no substantial advantage was gained through j substituting the pigment-type colorant for the dye-type colorant j j in ordinary ball pen inks insofar as erasability was concerned. j i i As stated above, if a writing medium is to be erasable, the colorant content therein, after being dispensed onto the paperj substratum, must remain in such a location that it can be readily j removed therefrom with a substantially non-abrasive eraser. Further, the colorant must not be allowed to affix itself either through chemical reaction or through ordinary physical attraction with any substantial degree of permanence to the written-upon surface. If these objectives are to be accomplished, the colorant: content of the writing medium must be prevented from penetrating ; 5 "7#- 200137 the pores of the substratum and must be shielded from intimate ] 1 contact with the solid members of the writinq surface. Further, if such a medium is to be dispensable from a ball point pen, it follows that the medium must possess physical characteristics | ^ J which do not differ widely from those of ordinary ball pen inks. i t Some success has been achieved in producing erasable ' ball point pen inks that are transitorily erasable, for example, 1 my prior U. S. Patent No. 4,097,290 hereinafter referred to as j Muller et al. and U. S. Patent No. 3,875,105 to Daugherty et al. ! Both of these patents teach the use of an elastomer. The Daughertv et al. patent teaches polyvinyl methyl ether and N-atftyn 2200 which is a synthetic rubber having a chemical structure like natural rubber is known, while my prior Muller et al. patent teaches natural rubber or rubber which essentially duplicates the chemical: structure of natural rubber. Both patents disclose the use of a volatile solvent. At this point it should be noted that the term : I "solvent" is beina used herein as a general term of art and not in: i J its specific technical sense to describe the vehicle into which ' large elastomer molecules, which may tend to remain in small ! clusters, are distributed and wherein the vehicle serves to carry : the elastomer molecules from within a ball pen cartridge onto the s substrate. \ i i i Daugherty et al. discloses the volatilizing component as being a solvent for the polyvinyl methyl ether matrix and having an evaporation rate of 3 to 15 on a relative numerical scale on I l which ethyl ether is assigned an evaporation rate of 1. Daugherty 2001 37 solvents for use as pigment dispersing agents or viscosity ' j adjustment solvents. My prior Muller et al. patent discloses a volatile low boiling orqanic solvent for the elastomer having a boiling point less than 180°C and exhibiting 100% evaporation within 60 minutes in combination with a non-volatile organic liquid solvent having a hi<jh boiling point in excess of 300°C. In: summary, both my prior Muller et al. patent and the Daugherty et V : J * 1 al. patent teach an erasable ink that includes the following: (1) the use of a pigment as a colorant; (2) an elastomer; and (3) i the use of mixtures of volatile and non-volatile solvents. ! Such prior attempts at an erasable ink have not been completely successful. One prior art method of making an erasable ink composition discloses a procedure in which a pigment paste is described as being stirred with a previously dissolved quantity of; natural crepe rubber has resulted in exceptional consumer detriments that include virtual non-writers, pens that show excessive oozing of ink during writinq and traces of ink that do not erase without damaqing the paper surface. 7 -XT- 200137 The below-listed prior United States patents are made of tp record herein. rJ PATENT NO. ISStJE DATE INVENTOR 2,715,388 August 16, 1955 Cofield, Jr., et 2,833,736 May 6, 1958 Glasser 2,852,397 September 16, 1958 Goesslinq 2,852,398 September 16, 1958 Goesslinq 2,853,972 September 30, 1958 Cofield, Jr. 2,956,038 October 11, 1960 Juelss et al. 3,099,252 July 30, 1963 Cofield, Jr. 3,425,779 February 4, 1969 Fisher et al. 3,875,105 April 1, 1975 Daugherty et al. 4,097,290 June 27, 1978 Muller et al. SUMMARY OF THE INVENTION A method for making and the composition for an initially erasable ink for a ball point writinq instrument which ink is characterized by its initial erasability by ordinary pencil erasers when applied by a ball point writing instrument to an absorbent paper Dr paper-like writing surface and which thereafter develops permanence. The method includes the steps of: (a) selecting elastomeric material from the group consisting of natural rubbers, synthethic rubbers and mixtures thereof; (b) masticating the selected elastomeric material by subjecting same to high shear 200137 stresses; (c) coloring said masticated elastomeric material by forced impregnation of colored pigments into said elastomeric material while subjecting same to further shear stresses; and, (d) mixing the pigmented elastomeric material with a solvent system that includes a volatile component and a substantially non-volatile low viscosity component to form an erasable ink composition. The erasable ink composition of the present invention comprises a pre-pigmented elastomer and a solvent system therefor. The solvent, system includes a volatile component and a substantially non-vrolatile component in which the volatile component has a boiling point less than 180*0 and said substantially non-volatile component i3 a low viscosity hydrocarbon oil, an essential oil, a petroleum derivative, a plasticizer or mixtures thereof having a boiling point less than 300°C and qreater than 180*C. The pre-piqmented elastomer is selected from the qroup consisting of pre-pigmented natural rubbers, pre-pigmented synthetic rubbers and mixtures thereof and j j preferably is a mixture of pre-pigmented natural and synthetic \ rubbers in approximately eaual amounts and is present in an amount j in the range of 1/3 to 2/3 by weight of the ink. j i i Therefore, it is the object of the present invention to j I produce an erasable ball point ink composition that possesses very smooth writing characteristics and that becomes permanent ouicker without compromising its short term erasability by ordinary pencil erasers. I i j It is the further object of the invention to achieve • smooth writing characteristics by utilizing a solvent system ! includes a substantially non-volatile component whic^i^is'*^ 1 'A I 200137 ! a low viscosity hydrocarbon oil having a viscosity ! in the range of 1-15 cps and a boiling point that is above 180*C ! and below 300 °C at atmospheric pressure. j I It is the further object of the present invention to ) restrict the presence of any non-volatile component of the solvent; system having a viscosity substantially above 15 cps and a boiling point above 300*C to an amount less than 15% of the weight of the i ink. I I \ l i i It is the further object of the present invention to | I produce an erasable ink compositon that comprises a pre-pigmented j i elastomer and a unique solvent: system that includes a volatile | j component and a substantially non-volatile component in which the j volatile component has a boiling point less than 180"C and j said substantially non-volatile component is at least i i a low viscosity hydrocarbon oil having a boiling point greater i than 180#C and less than 300*C. The pre-pigmented elastomer is ! selected from the group consisting of pre-pigmented natural j rubbers, pre-piomented synthetic rubbers and mixtures thereof and , preferably is a mixture of pre-pigmented natural and synthetic 1 rubbers in approximately equal amounts and is present in an amount: in the range of 1/3 to 2/3 by weight, of the ink. i ! It is the further objective of the present invention to j utilize a unique method of manufacture that includes the steps of , (a) providing a pre-pigmented elastomer component in which pigment, is substantially homogeneously distributed throughout and 200137 the elastomer component with molecular chain-attached pigment in a solvent system, the solvent system comprising a volatile component which contributes to initial erasability of the ink and a substantially non-volatile component which contributes to development of permanence of the ink; and {c) controlling initial erasability of the ink composition and capability of subsequently developing permanence when applied to the writing surface with the writing instrument by selecting, for the elastomer component, i | elastomeric materials which exhibit predetermined molecular weight I | distribution over a wide molecular weight range. ( i j DESCRIPTION OF THE ILLUSTRATIVE EMBODIMENTS i i b I In this invention, a truly smooth writing erasable i 1 writing medium has been obtained by uniquel/ combining selected materials in selected quantities and which utilizes pigmented j elastomeric material and a solvent system that includes a sub-I | stantially non-volatile low viscosity medium boiling component, i | while eliminating or drastically limiting the presence of a j certain heretofore utilized material, namely, a non-volatile high boiling organic solvent or plasticizer, so as to produce a writing medium which can be successfully dispensed in a ballpoint pen and which is formulated and functions as described hereinbelow. The Improved Erasable Ball-Pen Ink Manufacturing Process • A better rubber compounding and subsequent ink mixing I process is hereinafter described. This is a process in which | cis-polyisoprenes are initially "masterbatched" on a two roll mill ! prior to solution. This process has been particularly successful, despite the high variability of the properties of rubbers, in deriving maximum degrees of ink performance and uniformly"" from if batch to batch. f's \ , 1' c \-,0 "vp V...« |l ^ 2001 3 7 Heretofore erasable ball-pen inks essentially consisting of rubber, pigments, solvents and additives are subject to having such consumer appeals as smoothness, erasability, color intensity, and cleanliness of writinq which appeals can be compromised I primarily by the variability of the types and methods of j processing rubbers and secondarily by the quality and uniformity I of piqment dispersion in the ink. The production of the present improved ball-pen ink depends on three primary factors besides its preferred formulation. First, filtering of such high viscosity inks is ! I impractical. Elastomers, and particularly natural j cis-1,4-polyisoprene, must thus be selected to have a certified J grading in regards to the amounts of included gel and non-rubber solid particles. Secondly, the elastomers must be correctly masticated. Hard rubber will cause the ink not to flow properly, soft rubber will cause the ink not to erase, or write cleanly. Once adequately masticated, the rubber must also remain indefinitely in that state. i I Thirdly, the correct method of coloration is important in insurinq the quality and uniformity of pigment dispersion. This should be of the maximum homogeneous type so that piqmentation can take place in the early part of the ink making j process, followed by complete integration with the remaining elements to eliminate color phase-separation, and to promote optimum erasability by having as many particles of pigment surrounded by or entrapped in as many elastomer molecules as -yp- 200137 practically possible. All else remaining constant, ink erasability and cleanliness of writing performance characteristics can only be controlled if the pigment is homogeneously dispersed in the elastomer matrix which is, in turn, homogeneously dispersed into the solvent or vehicle to provide an ink having the desired j viscosity so that it will not initially penetrate into the paper j i fibers. Because of their small particle size, approximately 0.05 I microns, piqments tend to divide equally between the solvent and ! i elastomer phases. If solvent containing pigments separates from ! the elastomer matrix either because of dispersion instability, or i j improper mixing, the viscosity of some localized regions of the j i I ink will be very low resulting in non-erasability concurrent with j ! smudgy writing quality. 1. Selection of the Optimum Types of Elastomers Although not restrained to using more than one specie of cis-polyisoprene, I have discovered that further insurance against material or process variability is provided by using 50/50 mixtures of Natsyn 2205 and SMR 5CV60, synthetic and natural rubbers respectively. It is preferable that the elastomeric material or materials chosen exhibit a predetermined substantially uniform molecular weight distribution over a wide molecular weight! range of about 100,000 to 900,000. With the objective of minimizing milling time, the synthetic and natural rubbers chosen are certified to have relatively law, and narrow (20 units) initial Mooney viscosities at 212°F. Unlike other synthetic and natural rubbers both Natsyn 2205 and SMR 5CV60 also have a low level of hard resinous gel particles and extr§jnely low levels of retained dirt (0.05% by i3 2 001 3 "J, weight maximum). It has been found as unique to erasable inks that the use of rubbers that have large gel phases present promotes ink phase-separation while those that have retained dirt cause stoppages during writing, e.g., Natural Pale Crepe, SMR5L Natural Rubber produce significant phase separation because their gel content is not controlled. 2. Mastication Procedure Using a two-roll rubber mill, each peptized elastomer is normally softened separately to the same Mooney viscosity range between 17 and 27, rather than for a fixed time. To provide an optimum balance between plasticity (for writing smoothness and permanence) and residual viscoelasticity (for erasability) the inherently narrower and wider molecular weight distribution types that prevail between synthetic and natural rubber are utilized as complementary safeguards against equipment operating variances. It is helpful during rubber mastication to add a peptizing agent, such as Pepton 44, activated dithio bis-benzanilide, manufactured by the Organic Chemicals Division of American Cyanamid, Bound Brook, New Jersey. A suitable type two-roll mill can be obtained from the Farrel Company located in Connecticut. Such a two-roll rubber mill (60" X 24") develops the following range of shear forces: Range: 2.0 X 10® to 2.0 X 107 kG. Metre sec (Newtons) or 1.3 X 106 to 1.3 X 107 fT. Pounds sec-2 (Poundals) The shear force formula for such a two-roll rubber mill is as follows: ->5- 2-001 3jd f = 2 y V R L (1/ho ~ Vhi ) F = total force on rolls y = viscosity of material V = surface speed of rolls R = radius of rolls L = length of rolls hi= initial thickness of "sheet". ho= minimum (nip) thickness of "sheet". Further changes in viscosity can be retarded by incorporating a small amount of anti-oxidant prior to coloration. A suitable anti-oxidant is AO 2246, 2-2 ethylene bis-[4-methvl-6-tertiary butyl] phenol, also manufactured by the Orqanic Chemicals Division of American Cyanamid, Bound Brook, New Jersev. 3. Incorporation of Color into Rubber Subsequent coloration using dry, pre-wetted or preferably pigmented pastes, is performed on the same two-roll mill. Although both premasticated rubber compounds can be combined, a normal procedure has been to color them separately (to minimize weighing errors), with a paste consisting of about 50% pigments dispersed in a rubber compatible vehicle. Suitable rubber compatible vehicles for the pigment paste have been found to include non-volatile high viscosity mineral oils having a viscosity in the range of 50-60 centipoise or more and plasticizers such as dioctyl phthalate, diisodecyl phthalate fS 2001 3 ! and tricresyl phosphate. Increased degrees of pigment dispersion ; have incidently been achieved by incorporating flushed pigments, along with the dry pigments and vehicles that comprise the paste formula which may also include an amount of hydrocarbon resin. (This is useful, particularly when working with relatively light : bodied liquids, such as Penreco 2251 oil having a viscosity of 1.45 cps and Penreco 2257 oil having viscosity of 1.5 cps.) By "flushed pigments", I mean viscous commercially available high : tinting strength pigment dispersions that are prepared by directly i replacing water from presscakes with hydrophobic vehicles such as joils, and varnishes. ! i j The high shear stresses that prevail between the rolls i as the rubber and pigment are combined provide for optimum i homogeneity. Continuous mixing, cutting and folding not only disperses the pigment, but pre-dissolves the rubber in the paste vehicle to aid subsequent ink mixing as well as preventing chain recombination on storage. Forced pigment impregnation also tends i ' I to distribute color uniformly among all the molecular chain lengths, to prevent localized aggregation onto shorter chains that would contribute to non-erasability by being more rapidly absorbed into the paper. 4. Ink Mixing Procedure Once all of the desired pigment has been incorporated, the colored masterbatches are stripped onto protective sheets of polyethylene until such time whence a batch of ink is ready to be /6 -I 200137 made. The approximately 18" X 8" X 1/2" sized strips are then cut and weighed for solution in appropriate solvents using a planetary j type mixer. A suitable planetary type mixer can be obtained from | i Ross & Sons Co., Inc. of New York. A 40-gallon mixer will develop! the following range of shear forces: j I i Range: 1.0 X 103 to 4.0 X 103 KG. Metre sec-2 (Newtons) I or 0.7 X 103 to 3. X lO^Ft. Pounds sec-2 (Poundals) Alternatively, mixing can be conducted in a sigma-blade j kneader mixer. Such a mixer in a 100 gallon size is generally ! capable of developing the following range of shear forces: j ! Range: 5.0 X 103 to 2.0 X 10^ KG. Metre Sec-2 (Newtons) j or 3.0 X 103 to 1.5 X 104 Ft. Pounds Sec-2 (Poundals) j | Additional pigment paste can be added during the mixing | cycle when the mixture of pigmented rubber and solvents have J attained a maximum viscosity (to take full advantage of the j i relatively higher levels of shear that exist in the mixing at maximum viscosity.) Because the walls of the mixing vessel are already coated with a relatively thick viscous layer of colored ; j ink, the likelihood of "free" paste remaining undispersed is j I minimized. Transfer of ink after a period of approximately three j hours mixing time is provided by the use of a diaphragm type pump.j It has been seen from the aforegoing that a sphere of action has been taken to ensure the production of an ink that is j i optimally suitable for the service conditions it will be required to meet. 200137 Summary The erasable ball pen ink manufacturing process of the i present invention has incorporated the following unique features: j i 1) pre-selected cis-l,4-polyisoprene rubbers of the correct ! molecular weight range have been pre-pigmented on a two-roll mill prior to solution: 2) the forced pigmentation has insured uniform distribution of pigment particles, or paste among the | rubber matrix; 3) the bulk of the pigmentation has been performed; on effectively higher shear equipment rather than in planetary or sigma blade ink mixers to provide for uniform ink coloration without substantially reducing the optimum plasticity and i viscoelasticity of the elastomeric matrix; 4) a pigmented paste j i is preferred to allow sufficient lubricity so that mixing on a j two-roll mill does not break down the elastomeric matrix below the optimum Mooney viscosity range; 5) the ink mixing procedure merely requires solution of masticated pre-pigmented elastomers for completion. ERASABLE INK COMPOSITIONS Smoother writing erasable ball-pen inks of the present invention have been prepared that eventually become permanent quicker and more efficiently without compromising short-term erasability with a pencil eraser by using very low viscosity solvents (1.0-15 cps) such as light bodied oils that are further characterized by having boiling points or ranges between 180°C and 30 0"C at atmospheric pressure. Furthermore, the content of vehicles whose viscosities are above 15 cps and that boil above 300°C is minimized, and when used are employed in amount less than 15 percent by weight of the total ink composition. l9 200137 The purpose of my study was to define the role of these very low viscosity solvents in terms of comparing their effect on ink performance to oils and plasticizers that are significantly more viscous and that boil above 300*C. More specifically, erasable ball-pen inks (particularly those that depend on very volatile solvents to confer erasability using rubbery elastomers) undergo rapid changes in viscosity as the ink film leaves the cartridge via the ball socket onto the writing paper. The performance of higher viscosity oilq and plasticizers, although useful for pigment dispersion as dispersants or plasticizers for rubbery elastomers and as aids to achieving eventual ink permanence, show a direct relationship between their much higher viscosity and the perceived decrease in writing smoothness and the increased lenath of time reouired to achieve satisfactory permanence. substantially non-volatile solvents, such as hydrocarbon oils, boiling between 180 and 300*C and having significantly lower viscosities than the rubber compatible oils and plasticizers that boil above 300*C heretofore employed has shown to be in good so prepared are smoother and achieve eventual permanence quicker without compromising short-term erasability, pigment dispersion and long terra ink stability. * The above formula is a standard physics formula describing the force necessary to remove a substance from a revolving ball, where: The. performance of erasable ball-pen inks utilizing agreement with the predictions of the equation ^ =■ .* Inks dv » rate of change of velocity dx " rate of change of distance F =» force. A ■ area. V » viscositv. 200137 Shear stresses between the exposed ball and socket-rim are efficiently reduced if the elastomer pigment matrix is flowing through the pen tip immersed in very low viscosity liquids (1-15 cps) rather than in relatively thicker vehicles (58-104 cps) such as dioctyl phthalate, diisodecyl phthalate or heavy mineral oils. It should be noted that the quantity of preferred volatile solvents (those boiling at about 94-120*C and evaporating in less than about 8 minutes) is rapidly diminishing as the ink film passes the socket rim onto the exposed surface of the ball. In other words, a relatively non-volatile oil such as 2257 from Penreco, which has a viscosity about 39 times less than dioctyl phthalate, offers the rubbery pigment matrix less resistance to flow with the concurrent perception of increased writing smoothness. Through the mechanism of capillarity, the elastomer/pigment-oil matrix also incurs less resistance in penetrating surface paper fibers, again with the resulting decrease in the length of time required to achieve the desired degree of permanence. It should be noted that the rate of capillary absorption is inversely proportional to the viscosity. Other advantages of using low viscosity substantially non-volatile solvents besides those discussed above are: less stringing, resulting in a cleaner line; less tendency to transfer because of increased penetration of ink into paper; and less tendency of increased writing drag because low viscosity oils or solvents insure against the negative effects of elastomer molecular weights that are higher than the optimum desired values for satisfactory ink manufacturing. 2001ZJ The acceptable range of components for the present invention has been found to be as follows: TABLE I: ACCEPTABLE RANGES OF COMPONENTS Components Elastomeric Polymer Colorant Volatile Solvent Non-vo1ati1e(low^yis-cosity solvervEITaving a boiling point at atmospheric pressure from 180°C and less than 300°C Non-volatile (hlghj) viscosity solveSt or a plasticizer havinq a boiling point at atmospheric pressure above 300 °C Lubricants Other Selected Type % Amount by Weight Natsyn 2205 (synthetic rubber) and/or SMR 5CV60 (natural rubber) 18 Pigment 10 - 28 - 22 One compatible with Polyisoprene and having a boiling point less than 180°C, such as Lacquer Diluent #6 8-30 Hydrocarbon Oil, Essential Oil, Petroleum Derivative, Plasticizer or Mixtures Thereof 21 - 50.5 Heavy Mineral Oil or Plasticizer Fatty Acids Hydrocarbon Resin 0 to less than 15 0 -0 - 5 4.5 The preferred range of components, percent by weight of the ink, has been found to be as follows: elastomeric polymer 23-26%, colorant 18-20%, volatile solvent 19-21%, non-volatile low viscosity solvent 26-31%, non-volatile high viscosity solvent less than 5%, and lubricants 2-3%. The elastomer is selected from the group consisting of natural rubbers, synthetic rubbers and mixtures thereof and preferably is a mixture of pre-pigmented natural and synthetic 20 013 rubbers in approximately equal amounts. The amount of weight of the pre-piqmented elastomer is calculated to include the combined amounts by weight of the pigment and the elastomer present; and, where a flush pigment or a pigment paste is used may also include in addition to the weight of the elastomer and pigment the combined amount by weight of any resin and high boiling solvent that may be present. The suitable amounts of such pre-pigmented elastomer may vary from 1/3 to 2/3 by weight of the ink. Insurance against material or process variability may be provided by using 50/50 mixtures of Natsyn 2205 and SMR 5CV60, synthetic and natural rubbers respectively. Alkali Blue, Phthalo Blue, Lithol Red, Red 2B, graphite, carbon black and Diarylide Yellow. The suppliers of such pigments are as follows: Examples of suitable pigments include Victoria Blue, TABLE 2: SUITABLE PIGMENTS AND THEIR SUPPLIERS Pigment Supplier and Location E. I. DuPont Wilmington. Delaware Victoria Blue Alkali Blue Sherwin-Williams Co Cleveland, Ohio Lithol Red Hilton Davis Cincinnati, Ohio Graphite Acheson Colloid Co. Port Huron, Michigan Carbon Black Cities Co. Akron, Oh io Red 2B. Phthalo Blue and Diarylide Yellow BASF Corp. Holland, Michigan 2C0137 Other colors will, of course, require the use of other pigments and there is no intent to limit the pigments to those listed. The only requirements of the pigments are that they import the desired color to the ink and that they are sufficiently fine to readily pass through the clearance between the ball and retaining lip of the ball point; i.e., approximately 5 microns or less. A preferred low boiling point or volatile solvent is Lacquer Diluent #6 supplied by Chem Central Company of Chicago, Illinois which has the property of being compatible with polyisoprene and has a boiling point between 94 *C - 120"C. Suitable volatile solvents for the purpose of the present ink composition are considered to be those compatible with rubber having a boiling point less than 180*C at atmospheric pressure and evaporating in less than 60 minutes. Included among the suitable volatile solvents are V M & P Naphtha having a boiling point range of 121-139*0 and 100% evaporation in 8.3 minutes, 360-66 Naphtha having a boiling point range of 154-173*0 and 100% evaporation in 4 2.1 minutes, as well as very volatile solvents such as hexane and pentane. Suitable non-volatile low viscosity solvents include liquids having a viscosity within the range of 1-15 cps and having a boiling point less than 300*C and greater than about 180*C and particularly include light bodied oils such as hydrocarbon oils and light mineral oils boiling between 180*0 and 300*0 and having a viscosity around 1.5 centipoise which viscosity is sufficiently low as to result in a final ink viscosity of between 1,000,000 and 4,000,000 centipoise. A preferred example would be Penreco 2 257 oil, a product of Penreco, headquartered in Butler, Pennsylvania, a division of Pennzoil Company of Houston^T&xas. if % Penreco 2257 oil has a viscosity of 1.5 centipoise at^S'^P^nd a boiling range of 220*C to 260*C. However, the npn-vo^Mle -t 200137 low viscosity component may also be a petroleum derivative such as kerosene having the aforesaid low viscosity and low boiling point? a low viscosity, low boiling point essential oil such as pine oil, a terpene alcohol; Or this component may be a low viscosity, low boiling point plasticizer such as dimethyl phthalate and KODAFLEX (TXIB) marketed by Eastman Kodak Company, Kingsport, Tennessee. Table 3 below presents a listing of the physical properties of such suitable non-volatile lov£ viscosity components, including 2257 oil. TABLE 3; PHYSICAL PROPERTIES OF SUITABLE NON-VOLATILE LOW VISCOSITY COMPONENTS MATERIAL VISCOSITY BOILING RANGE VOLATILITY (25 °C) (760 mm) (100% Evaporation rate *) 2251 Oil 1.4 5 cps 190-260 °C >1200 minutes 2257 Oil 1.50 cps 222-260 °C >1200 minutes Kerosene 1.50 cps 164-279"C >1200 minutes Pine Oil 1.50 cps 206-220 °C >1200 minutes Magie 470 Oil 1.55 cps 239-269 °C >1200 minutes Magie 543 Oil 1.60 cps 236-277 °C >1200 minutes Kodaflex (TXIB) 2.0 cps 278°C slow >2000 minutes Dimethyl Phthalate 13.6 cps 282°C slow >2000 minutes * As measured on a Shell "EvapoRater". 200137 A suitable non-volatile, high viscosity solvent or plasticizer may be chosen from any one of the compounds listed in Table 4 below, but typically include plasticizers and heavy mineral oils having boiling points in excess of 300"C. TABLE 4; PHYSICAL PROPERTIES OP TYPICAL HIGH VISCOSITY COMPONENTS MATERIAL VISCOSITY BOILING POINT VOLATILITY D15 Mineral Oil Dioctyl Phthalate Gulf 562 Oil Di isodecyl Phthalate Tricresyl Phosphate 58 cps 385*C* very slow > 5000 min. 58 cps 386"C very slow > 5000 min. 60 cps 394®C* very slow > 5000 min. 88 cps 410*C very slow > 5000 min. 104 cps 420*C very slow > 5000 min. * Average boiling point of boiling point range. SOURCES FOR MATERIALS & DATA Mineral Oils: 1. Penreco; Los Anqeles, California 2. Magie Bros. Oil Company; Los Angeles, California Plasticizers and Solvents: 1. The Solvent and Chemical Companies; Los Angeles, California 2. Eastman Kodak; Kingsport, Tennessee Suitable lubricants are those usually included in ballpoint pen ink formulations and include fatty acids such as oleic, stearic and lauric acids. Where hydrocarbon resins are shown, a suitable hydro-carbon resin is Nevchem 140 manufactured by Neville Chemj^c^l ' Company, Pittsburgh, Pennsylvania. 200137 The following examples are illustrative of preferred embodiments but should not be construed in any way as limiting the present invention. In these examples components designated as volatile solvents have a boiling point less than 180°C at atmospheric pressure and the non-volatile low viscosity solvents have a viscosity of 1-15 cps and a boiling point ranging from 180°C to 300°C. The non-volatile substantially high viscosity solvent or plasticizer has a viscosity of 58 cps or more and a boiling point greater than 300°C at atmospheric pressure. EXAMPLE I - COLOR BLUE Components Elastomeric Polymer Cis-1,4-Polyisoprene Selected Type %_ % Amount by Weight 24 Colorant Pigment (50/50-alkali blue and victoria blue) 18 Volatile Solvent Lacquer Diluent #6 28.5 Non-volatile low viscosity solvent 2257 Oi1(1.5 cps) 21 Non-volatile substantially high viscosity solvent or plasticizer Dioctyl Phthalate 3.5 Lubricants Mixture of Oleic, Laurie and Stearic Acids (1,2,2) 5 100 -srf- 2 001 3^ EXAMPLE II- COLOR BLUE Components Elastomeric Polymer Colorant Volatile Solvent Non-volatile low viscosity solvent Non-volatile substantially high viscosity solvent or plasticizer Lubricant Selected Type Cis-1,4-Polyisoprene Pigment (50/50-alkali blue and victoria blue) Lacquer Diluent #6 2257 Oil (1.5 cps) Heavy Mineral Oil (Gulf 562) Oleic Acid % Amount by Weight 22 17 8 49.5 2.5 1 100 EXAMPLE III -COLOR BLUE Components Elastomeric Polymer Colorant Volatile Solvent Non-volatile low viscosity solvent Non-volatile substantially high viscosity solvent or plasticizer Lubricant Other % Amount by Weight Selected Type Cis-1,4-Polyisoprene 24 Pigment (50/50-alkali blue and victoria blue) 18 Lacquer Diluent #6 8 2257 Oil (1.5 cps) 30 Dioctyl Phthalate 14 Oleic Acid 2 Hydrocarbon Resin 4 100 27. -&T- ^ G01 Components |Elastomeric Polymer |Colorant Volatile Solvent Non-volatile low viscosity solvent Non-volatile substantially high viscosity solvent or plasticizer Lubricants EXAMPLE IV ~ COLOR RED Selected Type Cis-1,4-Polyisoprene Pigment (Red 2B) Lacquer Diluent #6 Magie 543 Oil (1.6 cps) % Amount by Weight 23.5 20.5 19 34.5 Mixture of Oleic, Laurie and Stearic Acids (0.5,1,1) 2.5 100 EXAMPLE V - COLOR BLUE ; Components | Elastomeric Polymer \Colorant Volatile Solvent Non-volatile low viscosity solvent Non-volatile substantially high viscosity solvent or plasticizer Lubricants Selected Type Cis-1,4-Polyisoprene Pigment (50/50-alkali blue and victoria blue) Lacquer Diluent #6 2257 Oil % Amount by Weight 23 16.5 22 35.2 50/50-01eic and Laurie Acids 3.3 100 2,9 -vf- Components Elastomeric Polymer EXAMPLE VI—COLOR BLUE Selected Type 50/50-Natsyn 2205 and SMR 5CV60 Colorant Volatile Solvent Non-volatile low viscosity solvent Non-volatile substantially hiqh viscosity solvent or plasticizer Lubricants Other 2-001 37 % Amount by Weight 23.2 Pigment (50/50-alkali blue and victoria blue Lacquer Diluent #6 2257 Oil Gulf 562 Oil Mixture of Oleic, Laurie and Stearic Acids (0.5,1,1) Hydrocarbon Resin 18.1 20.5 26.3 4.9 2.5 4.5 100.0 EXAMPLE VII - COLOR BLACK Components Elastomeric Polymer Colorant Volatile Solvent Non-volatile low viscosity solvent Non-volatile substantially high viscosity solvent or plasticizer Lubricants Other Selected Type 50/50-Natsyn 2205 and SMR 5CV60 % Amount by Weight 24.1 Pigment (80/20-carbon black and alkali blue) Lacquer Diluent #6 2257 Oil Gulf 562 Oil Mixture of Oleic, Laurie and Stearic Acids (0.5,1,1) Hydrocarbon Resin 19.1 20 26.2 4.5 2.5 3.6 100 .0 *7 137 EXAMPLE VIII-COLOR BLUE Components Elastomeric Polymer Colorant Volatile Solvent Non-volatile low viscosity solvent Selected Type Natsyn 2200 % Amount by Weight 22 Pigment (50/50-Alkali blue and victoria blue) Lacquer Diluent #6 2257 Oil Non-volatile substantially high viscosity solvent or plasticizer Gulf 562 Oil Lubricant Other Oleic Acid Hydrocarbon Resin 18 8 42 5 1 4 ToTT EXAMPLE IX-COLOR RED Components Elastomeric Polymer Colorant Volatile Solvent Non-volatile low viscosity solvent Non-volatile substantially high viscosity solvent or plasticizer Lubricants Selected Type 50/50-Natsyn 2205 and SMR 5CV60 Pigment (Red 2B) Lacquer Diluent #6 2257 Oil Plasticizer (diisodecyl phthalate) Mixture of Oleic, Laurie and Stearic Ac id s (0.5,1,1) % Amount by Weight 26 19 19 30.5 2.5 100 10 ^ZIQOZ Z.OO I 37 Components Elastomeric Polymer Colorant Volatile Solvent Non-volatile low viscosity solvent Non-volatile substantially high viscosity solvent or plasticizer Lubricants Other EXAMPLE X - COLOR GREEN Selected Type 50/50-Natsyn 2205 and SMR 5CV60 % Amount by Weight Pigment-Phthalo Blue Diarylide Yellow Lacquer Diluent #6 2257 Oil Gulf 562 Oil Mixture of Oleic, Laurie and Stearic Acids (0.5,1,1) Hydrocarbon Resin 24 12 7 19 29 3.5 2.5 _J 100 EXAMPLE XI - COLOR BLUE BLACK Components Elastomeric Polymer Colorant Volatile Solvent Non-volatile low viscosity solvent or plasticizer Non-volatile substantially high viscosity solvent or plasticizer Lubricants Selected Type Cis-1,4-Polyisoprene Pigment-Carbon Black Alkali Blue Lacquer Diluent #6 Kodaflex TXIB 2251 Oil 2257 Oil Dioctyl Phthalate Mixture of Oleic, Laurie and Stearic Acids (0.5,1,1) % Amount by Weight 23.5 17 5 18 10 10 9.5 4.5 2.5 100 -J*- </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 200137 EXAMPLE XII-COLOR BLUE Components Selected Type % Amount by Weight Elastomeric Polymer Natsyn 2200 24 Colorant Pigment (victoria blue) 11 Volatile Solvent Lacquer Diluent #6 30 Non-volatile low viscosity solvent 2257 Oil 33 Non-volatile substantially high viscosity solvent or plasticizer 0 Lubricant Oleic Acid 2 100 The ballpoint pen inks of this invention are more j viscous than the customary glycol based ballpoint pen inks and therefore are more suitable for use in a pressurized cartridge. j The exact pressure required will be dependent upon the opening i between the ball and lip of the point used, the viscosity range ofj the final ink composition, and the amount of ink and volume of the' tube used to contain the ink. It has been found that one i desirable ink pressure medium is compressed air. | i The pressurized cartridge utilizes a solid piston that j is positioned on top of the ink supply and forwardly of the j pressure producing medium. The follower has a central section ; that is cylindrical in shape and has its two ends formed as j conical portions so that no specific orientation in assembly is ! required. ; It is to be understood that the form of the invention herein above shown and described is to be taken as the preferred examples of the same, and that various changes in the components and the quantities thereof may be resorted to, without departing from the spirit of the invention or scope of the appended claims. 3Z--33- 33 WHAT WE CLAIM IS: 200137 I. A method of making an ink composition which is characterized by initial erasability by ordinary pencil erasers of a trace thereof when applied by ball-point writing instrument to an absorbent paper or paper-like writing surface and which trace thereafter develops permanence, said method comprising the steps of: (a) providing a pre-pigmented elastomer component in which pigment is substantially homogeneously distributed throughout and aggregated onto molecular chains of elastomer component; (b) dispersing the pre-pigmented elastomer component in a solvent system, the solvent system being present in amount sufficient to provide an ink composition having a viscos- 6 6 7-5Pc" lty xn the range of 1 x 10 - 4 x 10 cpsAand oanprising a volatile component having a boiling point less than 180^C and which contributes to initial erasability of an applied trace of the ink composition and a substantially non-volatile component which contributes to development of permanence of the applied trace; and composition and capability of subsequently developing permanence when applied as a trace to the absorbent writing surface with the ball-point writing instrument by selecting, for the elastomer component of step (a), elastomeric materials which exhibit predetermined molecular weight distribution over a wide molecular weight range and by milling the pigment into the elastomer component in the absence of the solvent system to provide the pre-pigmented elastomer component of step (a> and by selecting, for the substantially non-volatile component of step (b), a liquid having a boiling point in the 0 ea-l" Z5°c.- range of 180-300 C and a viscosity in the range of l-15cpsA —i (c) controlling initial erasability of the ink r 34 - 200137
2. A method as defined in claim 1 wherein said elastomer component consists of natural and synthetic rubbers milled to a Mooney viscosity of from 17 to 27 prior to the incorporation of pigment.
3. A method as defined in claim 2 wherein the elastomer component has a molecular weight range of 100,000 to 900,000.
4. A method as defined in claim 3 wherein the elastomer component has a molecular weight distribution which is substantially uniform over said molecular weight range.
5. A method as defined in claim 1 wherein the control of step (c) is also effected by providing, as the volatile component of step (b), a low boiling point solvent having a boiling point less than 180°C in amount of 8 to 30% by weight of ink and, in the substantially non-volatile component, 21-50.5% by weight of ink of low viscosity hydrocarbon oil having a boiling point less than 300^C and greater than 180°C.
6. A method of making an ink composition which is characterised by its initial erasability by ordinary pencil erasers when applied by a ball-point writing instrument to an absorbent paper or paper-like writing surface and which thereafter develops permanence, said method comprising the steps of: (a) selecting elastomeric material from the group consisting of natural rubbers, synthetic rubbers and mixtures thereof, said elastomeric material having a low level of hard resinous gel particles and an extremely low level of retained dirt which is no more than .05% by weight; - 35 - 200137 (b) masticating said selected elastomeric material by subjecting same to high shear stresses within the range of 2.0 x 10^ to 2.0 x 107 KG. Meter sec 2 (Newtons) to soften said elastomeric material to a Mooney viscosity within the range of 17 to 27; (c) colouring said masticated elastomeric material by introducing coloured pigment into said masticated elastomeric material while subjecting same to further shear stresses so as to forcibly impregnate said material with pigment, said colour pigment being selected from the group consisting of dry pigment, flushed pigment and a paste consisting of pigment dispersed in a rubber compatible vehicle, said forced impregnation thereby distributing colour uniformly among the various chain lengths of said elastomeric material; and (d) mixing said pigmented elastomeric material with a solvent system to form an erasable ink composition having a 6 6 2.5°C-, viscosity in the range 1 x 10 - 4 x 10 cps said solvent system comprising a volatile component and a substantially non-volatile component in which the volatile component has a boiling point less than 180^C and said substantially nonvolatile component is a low vicosity hydrocarbon oil having a+ zs° c a viscosity in the range l-15cpsAand a boiling point less than 300°C and greater than 180°C, and which includes less than 15% by weight of the erasable ink composition of a high viscosity material having a boiling point greater than 300®C,
7. A method of making an ink composition which is characterized by initial erasability by ordinary pencil erasers of a trace thereof when applied by a ball point writing instrument to an absorbent paper or paper-like writing surface and which trace thereafter develops permanance, said method com- """ prising the steps of: ' - 36 - 200137 (a) milling a pigment into elastomer to provide a pre-pigmented elastomer component in which pigment is substantially homogeneously distributed throughout and aggregated onto molecular chains of elastomer; (b) dispersing the pre-pigmented elastomer in a solvent system, the solvent system being present in amount sufficient to provide an ink composition having a viscosity 6 6 a>r 2S,oc" in the range of 1 x 10 - 4 x 10 cpsAand comprising a volatile component having a boiling point less than 180^C and which contributes to initial erasability of an applied trace of the ink composition and a substantially non-volatile component which contributes to development of permanence of the applied trace and writing smoothness of the ink composition when applied as a trace, said volatile and substantially nonvolatile components being solvents for the elastomer component and said substantially non-volatile component having a sufficiently low viscosity as to result in ink composition having a viscosity in said range thereof.
8. A method defined in claim 1 wherein said pre-pigmented elastomer component is provided by first milling the elastomer component to a selected Mooney vicosity range and then adding pigment to such milled elastomer component and continuing such milling until the pigment is substantially homogeneously distributed throughout and aggregated onto molecular chains of the elastomer component.
9. A method as defined in claim 8 wherein said elastomer component consists of substantially equal amounts of natural and synthetic rubbers milled to a Mooney viscosity of from 17 to 27 prior to the incorporation of pigment.
10. A method defined in claim 1 or 8 wl substantially non-volatile component having a vis ' « mm 2.00137 the range l-15cps at 25°c and a boiling point in uW 180-300°c also has a 100% evaporation rate of more than 1200 minutes and is present in amount of 21-50.5% by weight of the ink composition.
11. A method as defined in claim 10 wherein the substantially non-volatile component is a hydrocarbon oil.
12. A method as defined in claim 11 wherein said substantially non-volatile component also includes a solvent present in an amount less than 15% by weight of the ink composition, having a viscosity greater than 58cps at 25°C and a boiling point greater than 300°C.
13. A method of making an ink composition which is characterized by initial erasability by ordinary pencil erasers of a trace thereof when applied by a ball point writing instrument to an absorbent paper or paper-like writing surface and which trace thereafter develops permanence said method comprising the steps of: (a) masticating elastomer component having a molecular weight distributed over the range of 100,000-900,000 until it is softened to a Mooney viscosity range of 17-27; (b) force impregnating pigment paste into the softened elastomer component until the pigment is distributed uniformly among all the molecular chain lengths of elastomer component, the paste comprising about 50% pigment dispersed in an elastomer-compatible vehicle; (c) dispersing the pre-pigmented elastomer in a solvent system, the solvent system being present in amount sufficient to provide an ink composition having a viscosity in the range of 1 x 106 - 4 x 106cps at 25cfc and ocnprisirig a volatile component having a boiling point less than 180®C ana which contributes to initial erasability of an applied trace - 38 - XOOI37 of the ink composition and a substantially component which contributes to development of permanence of the applied trace, said volatile and substantially non-volatile components being solvents for the elastomer component and said substantially non-volatile component having a sufficiently low viscosity as to result in a final 6 6 ink viscosity within said range of 1 x 10 - 4 x 10 cps at 25°C.
14. An ink composition made by the method of claim 1, 6,7 or 13.
15. A ball point writing instrument containing an ink capable of depositing a trace on an absorbent paper or paper-like writing surface having minute voids therein, said trace being characterized by initial erasability thereof by ordinary pencil erasers and developing permanence, said ink comprising pre-pigmented elastomer dispersed in a solvent system, said pre-pigmented elastomer comprising a pigment and an elastomer component in which the elastomer component has a Mooney viscosity within the range of 17 to 27 and the pigment is force impregnated into the elastomer component prior to the pre-pigmented elastomer being dispersed in the solvent system, said pre-pigmented elastomer comprising 1/3 to 2/3 by weight of the ink and said solvent system comprising a volatile component and a substantially non-volatile component both of which are solvents for the elastomer component and in which the volatile component has a 100% evaporation rate of less than 60 minutes and said substantially non-volatile component has a 100% evaporation rate of more than 1200 minutes, said volatile component being present in amount of 8 to 30% by weight of the ink, said substantially non-volatile component being present in amount of 21-50.5% by weight of the ink and having a viscosity which is sufficiently low as to result in a final ink viscosity^of,,between o 1 x 10b - 4 x 10 cps at 25 C. /<T r A r 18 SEP 1985"' '* - 39 - 200137
16. A ball point writing instrument as defined in claim 15 wherein said pre-pigmented elastomer is selected from the group consisting of pre-pigmented natural rubbers, pre-pigmented synthetic rubbers and mixtures thereof.
17. A ball point writing instrument as defined in claim 16 wherein said pre-pigmented elastomer comprises a mixture of natural and synthetic rubbers in approximately equal amounts.
18. A ball point writing instrument as defined in volatile claim 15 wherein said substantially / component has a viscosity o range of l-15cps at 25 c.
19. A ball point writing instrument as defined in claim 18 wherein said substantially non-volatile component contains a solvent present in an amount of less than 15% by weight of the ink having a viscosity of greater than 58cps^and a boiling point of 300 C at atmospheric pressure.
20. A ball point writing instrument as defined in claim 15 wherein said substantially non-volatile component comprises a low viscosity hydrocarbon oil.
21. A ball point writing instrument as defined in claim 20 wherein said hydrocarbon oil has a viscosity in the range of l-15cps at 25°C.
22. An ink composition as claimed in claim 9 substantially as specifically described herein in any one of examples I to XII.
23. A method of making an ink composition as claimed in claim 1 substantially as specifically described herein. - 40 - 200137
24. A ball point writing instrument as claimed in claim 15 substantially as specifically described herein in any one of examples I to XII. SCRIPTO INC </div>